Composition of matter



I Patented Oct. I, 1940 PATENT OFFICE COMPOSITION or MATTER Melvin Dc Gr'oote, University City, and Bernhard Kaiser and Charles M. Blair, Ja, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd, Wilmington, Del., a corporation of Delaware No Drawing. Original application May 9, 1938, Serial No. 206,906. Divided and this application July 14, 1939, Serial No. 284,504

. '7 Claims. This invention relates to a new material or composition of matter, that is particularly adapted for use in the treatment of' emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the water, our present application being a division of our application Serial No. 206,906, filed May 9,1938, which has matured as U. S'Paten't No. 2,176,704, dated October 17, 1939. In addition to being particularly adapted for use as a demulsifier, in the 'resolutionof crude oil emulsions, said new material-or composition of matter may have uses in other arts that we have not investigated.

The new material or composition of matter which constitutes the subject-matter of our present' application, consists of a complex ester derived by reaction between (a) a certain kind of.-

complex amine derived, from blown oils and either primary or secondary hyd'roxy amines;'

and (b) polybasic carboxylic acids. Said new compound or-composition of matter may be used either alone, or in admixture with conventional demulsifying agents of a compatible type.

In using said material to.break petroleum emulsions of the water-in-oll type, the emulsion is subjected to the action of a demulsifying agent consisting of said material, thereby cansing the emulsion to break down and separate into its component parts of oil and water or brine when the emulsion is permitted to remain inv a quiescent state, after treatment, or is subjected to other equivalent separatory procedure.

As previously indicated our new material or composition of matter is derived by reaction between a polybasic carboxy acid or its functional equivalent, such as an anhydride, and a complex amine of the kind-derived by reaction between a primary or secondary hydroxy amine and a blown oil. Polybasic carboxy acids include phthalic acid, maleic acid, malic acid,'succinic acid, adipic acid, etc. Since the complex amine derived from a primary or secondary hydroxy amine and a blown oil is not a well-knownarticle of commerce, we will hereinafter describe the same in detail. In this connection, attention is called to our copending application Serial No. 206,900, filed May 9, 1938, whichhas matured as U. S. Patent No.

2,167,346, dated July 25, 1939, which is concerned.

with breaking petroleum emulsions, by means of such complex amines. I

Attentionis directed to. the fact that in describing the manufacture of new composition of matter which constitutes our present invention, an esteriflcation process may appear at three different stages;

In the first place, if one had a blown fatty acid instead of a blown oil, such acidic material could be esteriiied in a. conventional manner with any alcohol, 1. e., ethyl alcohol, ethylene glycol, or

glycerol, by means of intimate mixture in the temperature above become combined with the oxy-acyl radicals of v the acidic materials present in the blown oil.

Thus, this particular'rearrangement is also an.

order to simplify the discussion herein included,

which is concerned with the manufacture of these new compositions of matter. The subjectmatter immediately following, which is concerned with the preparation oi the complex amine, is taken substantially verbatim from our co-pending application, Serial No. 206,900, filed May 9, 1938, which has matured as U. S. Patent No. 2,167,346, dated July 25, 1939.

The complex amines, which are subsequently subjected to polybasic carboxy esterification, are

derived from blownoils. ,It has long been known that various animal, vegetable, and marine oils can be blown or oxidized so as to yield materials which difier' in chemical and physical properties and characteristics from the parent materials from which they were derived. The oxidation process is-generally conducted by means of moist or dry air, ozone, ozonized air, or a mixture of the same, It maybe conducted at atmospheric pressure, or may be conducted under increased pressures of several atmospheres or more. 0x1- dation may be conducted at relatively low temperatures, for instance, 100 or 130 C., or may be conducted at a much higher temperature. Oxidation'may be conducted in absence of catalysts, or in presence of catalysts. Such catalysts mayconsist of metallic salts, such as oobalt or manganese oleate, or may consistof or-' ganic materiaLsuch as alpha pinene or the like.

Oxidation may be conducted in'a. relatively short time, such as 20 hours, or may require 200 hours or more.

The blown or oxidized oils are generally selected from unsaturated oils of the non-drying type, or the semi-drying type, including the marine oils, such as marine mammal oils, etc. They are rarely selected from the active drying oils, such as linseed oil and-perilla oil. Although glycerides of saturated acids, such as stearin or palmitin may be oxidized, such blown materials are rarely employed in the various arts. Oxidation of the active drying oils, such as linseed oil or perilla oil, is generally apt to yield a solid or almost solid product, and as aresult the complex amines are rarely-produced from such materials alone, but may be produced from a mixture of oils containing some proportion of such active drying oils. oils of the kind employed in various industries, such as the demulsiflcation of petroleum emulsions, are derived from castor oil, rapeseed oil, cottonseed oil, peanut oil. corn oil, olive oil, and various marine oils, such as sardine, herring, sperm, menhaden. and pilchard oil.

When an unsaturated fatty acid or oil, for instance, olive oil, is blown or oxidized with air,

hydroxyl groups are formed at the ethylene linkage. This is particularly true if oxidation is carried out with moist air. It is believed that oxygen is first absorbed so as to saturate the ethylene linkage, and that further reaction takes place with water to produce two hydroxyl groups. Whether or not this is the correct explanation, it is known that hydroxyl groups are formed. For instance, Chemistry of the Oil Industry, by Southcombe, 1926, page 181, in speaking of blown (oxidized) oils, states as follows:

- Hydroxyl groups are unquestionably formed,

as the considerable rise in acetyl value proves."

Patents which describe conventional blown oils or conventional methods of making various blown oils for various purposes (including in in some instances, for the purpose of demulsifying crude oils), include the following:

U. S. Patent No. 1,929,399, dated October 3, 1933, to Fuchs; U. S. Patent No. 1,969,387, dated August 7, 1934, to Tumbler; U. S. Patent No. 2.023,979, dated December 10, 1935, to Stehr; U. S. Patent No. 2,041,729, dated May 26, 1936, to Seymour, and U. S. Patent No. 1,984,633, dated December 18, 1934, to De Groote and Keiser.

Since a very suitable form of a complex amine from the standpoint of subsequent polybasic carboxy esterification, is derived from blown castor oil, as a primary raw material, an effort will be made to describe this product in considerable detail. Mild oxidation of castor oil (see Chemical Technology and Analysis of Oils, Fats and Waxes, by Lewkowitsch, 6th edition, vol. 2, p. 406) produces relatively small modifications in certain important chemical indices, such as the iodine value, the acetyl value, and the saponification value. either by continued mild oxidation from the very beginning of thereaction, as induced by either a higher temperature of reaction, or the presence of a catalyst, such as alpha pinene, manganese ricinoleate, etc., then one obtains an oxidized oil having characteristics which clearly indicate that drastic oxidation has taken place. These indices of drastic oxidation are a relatively low iodine value, such as 65 or less, and may be as low as 40 or thereabouts; an acetyl value of approximately to 200; an increased viscosity; a specific gravity of almost 1, or even a trifle over 1 at times; and in absence of other 00 011 3 matter, a deep orange color.

In actual practice, blown If drastic oxidation takes' place,

purchased on the open market under various trade names, such as blown castor oil, bodied castor oil, blended castor oil," blended bodied castor bil," processed castor oil, oxidized castor oil, heavy castor oil, "viscous castor oil, etc. These various names appear to be applied to drastically oxidized castor oils which are different in degree but not different in kind.

Not only may blown oils be derived by direct oxidation of the various fats and oils, but also by direct oxidation of the fatty acids. Blown ricinoleic acid may be derived in the manner indicated in U. S. Patent No. 2,034,941, dated March 24,1936, to De Groote, Keiser and Wirtel. It should be noted that blown oils in the broad generic sense herein employed include not only the products derived by oxidation, but also the products derived by polymerization. Reference is made to polymerized ricinoleic acid described in U. S. Patent No. 1,901,163, dated March 1, 1933, to Hinrichs. Reference is also made to polymerized castor oil or similar oils of the kind disclosed in application Serial No. 59,090, filed J anuary 13, 1936, by Ivor M. Colbeth, Patent 2,114,651 issued April 19, 1938. It might also be desirable to point out that the expression blown oil," as herein used, contemplated blown unsaturated liquid waxes, such as blown sperm oil. It is understood that in the appended claims the expressions blown oil "or blown oil fatty acids" are used in this broad sense to include all the various materials, such as esterified. blown fatty acids.

In such instances where blown orpolymerized acids are used, it will become apparent that these materials must be converted into an ester before reaction with an amine, as subsequently described. For instance, blown castor oil fatty acids, or polymerized ricinoleic acid can be converted into the ethyl ester, methyl ester, propyl ester, cyclohexyl ester, ethylene glycol ester, glyceryl ester, or any suitable ester, by means of conventional esterification processes. We desire specifically to point out that the estolides of blown oils, as described in U. S. Patent No.

2,079,762, dated May 11, .1937, to De Groote and Keiser, are not suitable to be employed in place of blown oils, even after conversion into a completely esterified material by means of a selected alcohol by conventional processes. We have found that when a blown oil is converted into an estolide, such product no longer contains the typical blown oil acidic'material. Such estoiides are not adaptable as raw materials for the manufacture of the complex amine employed in the final polybasic carboxy esteriflcation'.

In preparing the intermediate raw material intended for esterification in the present invention, we prefer to produce an amine by reaction with a drasticallyoxidized castor oil having approximately the following characteristics Our usual procedure is to eliminate carboxylic acidity of a blown oil by means of a conventional 'esterification reaction. For instance, in referring to the analysis of the blown castor oil above, it will be seen that such product contains acidity equivalent to -10% of the total saponifiable value. Such acidity can 'be removed by esterification with an alcohol such as methyl'alcohol, ethyl alcohol, propyl alcohol, etc. On the other hand, since'glycerine is the naturally-occurring alcohol. present in most oils and fats, and

The typical reactions of fatty acids and amines,

particularly primary or secondary amines, may be indicated by the following:

(A) Salt formation R.COOH+R'NHH [HHR'N.H]OOC.R (B) Amide formation a.cooH+rm'NH-+Rco.NR'H

aldehydic acids are present, certain amines, particularly primary or secondary amines, can enter into reactions which are characteristic of the,

aldehyde radical and would have no connection whatsoever with blown oils which do not contain aldehydic acids. It'is to be noted that as far as we are aware, the blown oils which we have employed in the manufacture of the preferred ln-,

termediate raw material intended for polybaslc carb'oxy'esterification, are free from any. aldehydic acids, and even if aldehydic acids are present, a complex amine of the kind hereincontemplated would not be formed by virtue of reaction with the aldehydic group alone. As to reactions of the type involved in the ammonolysis of aldehydic acids, reference is made 'to U. S. Patent No. 2,079,764, dated May 11, 1937, to De Groote and Kaiser.

(Ei Still another type of reaction involves fatty acids and a tertiary alkylolamine or its functional equivalent, such as a. tertiary hydro'xyalicyclic amine. Such reaction may be iiidicatedin the following manner:

resultant materials are estolides, rather than the unaltered fatty acids. This has been pointed out,

in the De Groote, Kelser and Wirtel patent to which previous reference has been made.

It is manifest that an effort .to react liberated blown oil fatty acids'w'ith triethanolamine, for

materials of the kind employed as the intermediate raw material intended for polybasic carboxy esterification cannot be obtained from liberated blown oil fatty acids, butmust be obtained from the blown oils themselves. This is comparable to the situation indicated in our copending application Serial No. 180,992, filed December 21,- 1937, in which it is shown that certain amines of a comparable type can be derived from triricinolein, di-ricinolein, monoricinolein, ethyl ricinoleate, and the like, but cannot be derived from ricinoleic acid because polyricinoleic acid would be formed.

We have discovered that if blown oils of the kind described are reacted in ester form with primary hydroxy amines or secondary hydroxy amines, one obtains materials of. the kind characterized by the fact that the fatty acid radicals derived from the blown oil are present in the aminecompound in an esterifled form. Such form is substantially unaltered as compared with the original form as present in the blown oil itself. It may be well to point out two facts in regard to the use of blown oils and the fatty acids derived therefrom. We have previously pointed out that ordinary blown oils show acidity, and that our present reaction is concerned between hydroxy tertiary amines and esters, and not fatty acids. However, since many conventional blown oils contain as little as 5% free.

acidity, calculated in the usual manner, it is obvious that this small acidity may be ignored and that for practical purposes, the preliminary step intended to insure complete esteriflcation may be eliminated.

Secondly, we have referred to the acids preseni? in blown oil as "fatty acids. This is purely a matter of convenience. The expression fatty acids, as usually employed, is intended to include unsaturated fatty acids of the kind which occur in naturaigpils and-fats in the form of esters, such as glycerides. These fatty acids are sometimes referred to as higher fatty acids, and occur in oils such .as olive oil, cottonseed oil, soy bean oil, cornoil, castor oil, neats-foot oil,

and in marine oils such as menhaden oil, her-- ring oil, sardine oil, pilchard oil, etc.

In some instances, these oils or the corresponding fatty acids, may be heated or oxidized so as to produce lower homologues or higher polymeric forms. For instance, ricinoleic acid can be heated in such a. manner as to'produce hendecenoic acid, 0111-1220:, which is 'a lower homologue of oleic acid. Such materials are not fatty acids in the usual sense, since they do not occur as such in natural oils and rats, but they are herein considered as fatty acids, since. they represent lower homologues or isologues, and have the characteristic properties of the common fatty acids, They occur in blown oils, obtained by well-known procedure. For instance, when castor oil is heated and oxidized so as to produce blown or oxidized oil, one may at least partially break down the molecule having 18 carhon atoms into two molecules having, for example, 7 carbon atoms and 11 carbon atoms, Such acids of lower molecular weight may combine in various maners to produce acids of' higher molecular weight than naturally-occurring may" higher orlower molecular weight which appear is the formation of amides.

cogenerically in conventional blown oils in the form of free acids or' esters.

- In view of the somewhat complicated chemical nature of the complex amines employed for polybasic carboxy esteriflcation it may be well to point out the general type of reaction involved in their manufacture. For convenience, the fatty acids of blown oils will be considered as R.COOH and the blown oil itself will be con? sidered as the glyceride of these materials and indicated thus: (R.COO):C:H5.

- Purelyas a matter of simplicity, diethanolamine will be selected as the primary or sec-' ondary hydroxyamine for reaction.with a selected blown oil." The-reactions taking place in varying molecular proportions may be indicated in the following manner:

OH.C1HA

R.COO 0 5.0111.

R.COO-C3H5+ aooo O H.C: e

OH.C:H&

srtco 0.0m.

' nn+oimwn i I OILCaHi on.o,n. R.COOC3H 011mm p.000

R.COO

oncii n ampoocmomnnoandonn R.COO' orLcnmNnH (III) .aooo-czmi-omclnmnn 3.000 OH-ClHINHH a.R.oo o.o,H.NnH+o.Hr on When acid esters derived from acids of relative- 1 low molecular weight, such as acetic acid, oxalic acid, etc., are treated with ammonia or primary or secondary amines, the usual reaction The tendency towards amidization decreases with the increase in the length of the carbon chain or the molecular weight 'of the fatty acid. We have found that perhaps due to the nature of the fatty acid radical present in blown oils, .or perhaps due to the larger molecular weight, or perhaps both rea- 1 sons, or even for other reasons, that treatment of blownxoils with basic non-aryl primary or secondary amines results in the formation to alarge or predominant degree of materials of the esterified form, indicated in the formulas immediately preceding. In a general way, esterification reactions take place at a temperature below. the point where amidiflcation takes place.

, In conducting the reactions one should select the lowest suitable temperature and conduct the reaction foran extended period of time, rather than employ a high temperaturrand a short stance, at

period of time. Such conditions make for a maximum of esterification and a minimum of amidiflcation.

The manufacture of these compounds is relatively simple. The selected blown oil and the 5 selected hydroxy primary or secondary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for in- C., and below the decomposition point of the amine or blown oil, for instance, 0., for a suitable period of time, such as 4 to 24 hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., maybe present in amounts of about .5% or less. It is to be noted that the blown oils are always in ester form' and are not in acid form, thus are not subiect to decomposition of the kind which occurs when one attempts dir'etlyto react a blown oil fatty acid with a tertiary alkylolam'ine. It is furthermore to be 20 noted that this reaction does not take place to any appreciable extent if the blown oil has been converted into a soap or salt. It is obvious that the blown oil fatty acids must be in the form of which all four hydrogen atoms of the ammonium radical Nm have been replaced by a hydrocarbon radical or oxy-hydrocarbon radical, as, for example, in trimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which must'berecognized is that these amine compounds are not amides. It has beenpreviously pointed out that an amide formation involves a product in which there is a direct linkage between the carboxylic carbon atom and the nitrogen atom in the amine. j Thisis not the case in the compounds employed as demulsifying agents in the present process.

In the third place, it must be recognized that these compounds are derived only from basic amines. The word basic" is employed to exclude amines having little or no basicity, such as the I ordinary aromatic amines, orany amine having 65 at least one aryl' radical directly joined to the amino nitrogen atom. For this reason, these amine products which are herein contemplated as demuisifying agents and which necessarily are characterized by freedom from any aryl groups 60 is an aryl group present, but it is not directly 5 attached to the nitrogen atom, as in the case of aryl amines, but infact, represents nothing more or less than a substituted alkylamine. For instance, we consider benzyla'mine as being the priinar'y amine, phenmethyl amine.

Finally, it must be recognized that these mav terials, have not lost any basicity in the forms of the esterifled amine, and that; they exhibit all .the properties of a basic amine, that is, they combine with water to form a base presumably 75 a substituted ammonium compound, but not a substituted quaternary ammonium compound, since there are always at least two unsubstituted hydrogen atoms of the ammonium radical present. They combine with various acids to form salts. For example, they may be combined with acetic acid, hydrochloric acid, lactic acrd'fhloracetic acid, nitric acid, butyricacid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid, to form salts. It is understood that the reference in the specification and appended claims to the amines includes the basic form and the acid salts, as well as the amines themselves. The characteristic properties of the final composition are contributed in part by the amine, and it is immaterial whether it be considered as being in any one of the following forms:

(rpm: TNHH 5 a "/H H mile-n a TN n on (T): -H H in which T- represents the substituents of the amino hydrogen radicals of the parent ammonia from which all amines are hypothetically derived, and X simply represents the acid radical of any acid employed. v

In referring to the complex amines derived by reactions involving blown oils and hydroxy priin which misi or 2 and m is o or l, with the mary or hydroxy secondary amines, it is to be noted that the products may be characterized by the following formulas:

proviso that m+m' =2; and n denotes any small whole number, preferably less than 10, and in the case of diethanolamine, denotes the member 2.

, In the above formulas and in all subsequent carbon atoms.

formulas, including those appearing in the apin whichacoo has the same significance as previously. l

It is also possible to obtaincompounds such as monoacetylated diethanolamine in which the acetyl radical has replaced one hydrogen atomv of one of the hydroxy ethyl radicals. Acetic acid in this instance may be considered typical of the lower fatty acids which have less than 7 If such monoacetylated dieth 'anolamine were employed, the reaction product would be indicated by the following type formula:

In this formula a'co indicates an acyl radical derived from a low molecular weight fatty acid 'esterifled blown oil fatty acids 'to produc'e the having less than 7 carbon atoms. Attention is: directed to the fact that the divalent aliphatic radical indicated by CsHm may be a radical such valent alkyl radical, it may be a monovalent alicyclic radical, such. as a cycloliiexyl radical, or it maybe an aralkyl radical, such asa benzyl radical. In the claims appended hereto, it is understood that the expression .alkylol' includes the hydroxy hydrocarbon radicals, whether derivedfrom alkyl, alicyclic, ,or aralkyl radicals. It is furthermore understood in the hereto appended claims that the expression hydroxy alkyl: includes hydroxy alicyclic as well as hydroxy aralkyl radicals, provided that in the latter the hydroxyl group is attached to the aliphatic side chain. Attention is also directed to the fact that the tertiary amines involving the glyceryl radical (CaI-IsOH): may substitute for the hydroiw alkyl radicals of the kind described. It is also understood that alkyl-oxy-alkyl radicals are the equivalent of an ordinary allgvl radical, insofar that they might appear in products such as the dihydroxy ethyl ether of diethanolamine, which may be indicated by the following formula:

(CaHsOCzHsOH) M. such material would be the obvious functional equivalent of diethanolamine in reactions of the kind'contemplated in the manufacture of the intermediate raw material intended for polybasic esteriflcation. The amine employed as a demulsifying agent in the present process'might v be indicated by the following formula:

12.0 1 iiiJi e in whichmis 1 or 2,-m' isOor 1, and m" is 1 or 2,

with the proviso that m+m'+m"'-:3; T is an alkyl radical or a radical of the type 1 or a hydroxy alkyl radical; and R'.COO' represents an acid radical having less,:than 7 carbon The expression alhl'fis used in the v atoms. broad sense p evicusly specified, and it is also repeated that he amine may be used in the form of the base or in the form of a salt.

{Suitable bases which may be reacted with blown oils or completely esterifled blown oils, or

reagents of the present inventioninclude 'di-' ethanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, -dipropanolamine, propyl propanolamine, monoglycerylamine, diglycerylamine, monoglyceryls amylamine, etc. Other examples include cyclohexylami-ne, dicyclohexylamine, cyclohexyl ethamines of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lacticacid, so as to form the lactyl derivative mula:

then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if the corresponding product derived from diethanolamine, provided that both hydroxy radicals had been esterified with lactic acid. If, on the other hand, diethanolamine were treated with lactic acid soas to give monolactyl diethanolamine of the following composition:

of the following for- L OH O then such compound would be included, due to the presence of the hydroxyl radicals attached to the alkylradicals.

The following examples indicate various means ,by which one can prepare complex amines of the kind which are suitable for polybasic carboxy esteriflcationz.

' Complex amine-Example I Blown castor oil of the kind previously described in detail is employed. For-the sake of convenience, its molecular weight is considered as being 1000. Commercial diethanolamine and blown castor oil in the proportion of one mole of blown castor oil to three moles of diethanolamine are heated to a temperature between 120 and 140 C. for about 12 hours. Loss of basicity is an indication of amidification. Time of reaction may be extended or temperature lowered or raised so as to insure maximum esterification.

Complex amine--Example II hexylamine. This product is substituted for diethanolamlne in Example I.

Complex amine-Example V Glycerylamine is substituted for diethanolamine in Example I.'

Complex amine-Example VI Triethanolamine is substituted for diethanolamine in Example I.

Complex amineExample VII Benzylamine is Jreacted with glyceryl monochlorhydrin to produce monoglyceryl benzylamine. This product is substituted for diethanolamine in Example I.

Complex amine-Example VIII An ether amine of the following composition: ciuiocumon 003.00.21.01! is substituted for diethanolamine in Example I.

Complex amine-Example IX Blown rapeseed oil of commerce, molecular weight figured as 990, is substituted for blown castor oil and employed in Examples I-VIII, inelusive.

Complex amine-Example X Blown cottonseed 011, molecular weight figured. as 980, is substituted for blown castor oil in Examples I-VII, inclusive.

It is obvious that the amines of the kind above described will contain hydroxyl groups attached to the fatty acid radical derived from blown oil, since all blown oils show a hydroxyl or acetyl value, and, as previously pointed out, such radicals appear without change in the complex amine. It has furthermore been indicated that the complex amine may'also have .a hydroxyl radical as part of an alkylol radical. In addition to this, there may be found hydroxyl radicals present, due to condensation with glycerol by means of an ether linkage. In any event, the complex amines of the kind above described are reacted with polybasic carboxy acids so as to pro-' duce an esteritlcation product, and preferably, an esterification product of the kind in which there is at least one residual carboxyl radical.

Esteriflcation is conducted in the conventional manner. The two materials are heated together at a temperature above the boiling point of water, for instance, 110160 (3., and agitated until esteriflcation has proceeded to the desired point. One may pass through a dried inert gas to hasten esterification, or esteriflcation may take place in an inert solvent, in which both components are mutually soluble, as, for example, xylol. Under such conditions the reaction is best conducted at the boiling point of the inert solvent, for instance, xylene, and after the reaction is complete the xylene is eliminated:

It is to be understoodthat although phthalic anhydride is the most desirable aromatic reagent, one may employ polybasic carboxy acids or their anhydrides, such as succinic acid, malic acid, fumaric acid, citric acid, maleic acid, adipic acid, tartaric acid, glutaric acid, diphenic acid, naphthalic acid, oxalic acid, suberic acid, pimelic acid, etc. In subsequent examples, phthalic anhydride will be employed, because in many instances it is most desirable to use the anhydride of anaromatic acid and also because phthalic anhydride is obtainable at a relatively low cost in a state of high technical purity. Furthermore, phthalic anhydride shows little or no tend-' ency to produce objectionable secondary reactions, and as a rule one obtains almost theoretical yields'of the desired products. It is understood, however, that any polybasic carboxy acid may be employed or any functional derivative thereof. It is also obvious that after reaction any free ionizable hydrogen atom can be neutralized in any suitable manner, for instance, by reaction with caustic soda, caustic potash, ammonia, any basic amine or the like, orby further esteriflcation with a monohydric alcohol, for example, such as methyl alcohol or ethyl alcohol, or with a dihydric alcohol, such as ethylene glycol, or a trihydric alcohol, such as glycerol. In view of this fact, the acid esters of carboxy acids, such as butyl hydrogen phthalate, propyl hydrogen phthalate, ethyl hydrogenv oxalate,

.etc., would be the functional equivalent of the polybasic carboxy acid itself.

Composition of "flatter -Example I The complex amine derived according to the directions under the heading .Complex amine- Example I is analyzed so as to determine its hydroxyl value, and also its average molecular weight. From these values a calculation is made so as to determine the proper amont of phthalic anhydride to add, based on the reaction permitting a residual carboxyl radical to remain. The

materials are intimately mixed and heated at approximately 120-160 C. with constant agitation until samples taken from the batch and analyzed showsubstantially complete disappearance of the hydroxyl valuel 7 Composition '0! platter-Example ll Instead of employing the complex amine of the .kind previously described under the heading "Complex amineExample III, substitution of other amines of the kind indicated under Complex amines-Examples II-V III inclusive, are

employed. I

Composition of nwtter-I-Ezample III Examples of the kind prepared according to "Composition ofmatter-Examples I and II, are

a modified by the employmentof maleic anhydride instead of phthalic anhydride.

I y Composition of matter -Example IV- In the example immediately preceding, oxalic acid is substituted for maleic acid with modifica- 40 tion so that the reaction is conducted at a lower temperature to prevent decomposition of the oxalic acid-for instance, 1l0-120 C.

Composition of-matter-Emmple v Products of the kind described in the example immediately preceding are prepared, but adipic acid is substituted for oxalic acid.

-We desire to emphasize that the products ob- I tained in the above examples may be used in the form of the amine by direct'contact with an emulsion without contact with water. They may be contacted with water, i. e., in the form of asolution, so as to produce in a greater or lesser degree the amine base. Furthermore, any of the products above described may -.be combined with a suitable acid. Aceticacid' may be employed.

Hydrochloric acid is P rticularly deslrable.- In some instances acids, such as oleic acid or mph- 'thenic acid, maybe employed to give a suitable salt. As previously pointed out. any carboxylic hydrogen atom maybe replaced by a suitable metallic atom or .an organic radical derived from an alcohol or from an amine. All such ionizable hydrogen atom equivalents are considered as the 5 functional equivalent of the ionizable hydrogen atoms themselves, and such neutralized forms are i'ncludedin the scopeof the appendedclaims as the equivalent of the acidic form. It is realized that where a free carboxyl and a basic amine 7o residue exist in the same molecule, there may be a tendency towards the formation of inner salts comparable to sulfanilic acid; but due to the size of the molecule involved and perhaps for reasons of steric hindrance, we are not aware that su 75 inner salts are formed.

. ing procedure.

= In examining the method of manufacture of these complex amines, as previously illustrated,

it is apparent that certain by-products appear as 'glycerin'e, monoor diglycerides, etc. From a practical standpoint it is unnecessary to separate these cogeneric materials, although it would be possible to do so by conventional processes. It is quite possible that these materials which appear as part of the reaction mass contribute to a.

greater or lesser degree to the demulsifying power of the final material as obtained after polybasic carboxy esteriilcation. It may be that some of these materials which appear in the reaction mass cannot be completely identified asto their form.

, For instance, it is at once possible to see that condensation products might be formed under proper conditions between complex amines of the kind employed and either glycerol or diethanolamine, by virtue of an ether linkage. Both glycerol and 1 diethanolamine maybe present in themanufac- I ture of some of the complex amines which are subsequently subjected to 'polybasic carboxy esterification. In viewoi this fact, in the ap-' pended claims the composition of matter or product herein contemplated will be described not only in terms of conventional chemical structure, but

also in terms of the method of manufacture. The

purpose of the claims which are characterized by reference to the method of manufacture is specifically to include the general reaction mass pro polybasic carboxy acid or its functional equivalent as described, and the complex amineof the kind described, in such a manner as to involve reactions other than salt formation. In other words, the complex amines are basic in nature, and therefore, could react with a polybasic carboxy acid, so as to form a salt in the manner indicated thus: I

' coon man'sr COOH I mmnmoocxacoom mnmmoo'om coonor Such reactions are purely salt formation. The

materials of the kind herein contemplated, re-

gardless of their nature, are of the kind otherthan salt formation.

We desire to emphasize that the expression polybasic carboxy acid" as it appears in the claims, refers'not only to the acid itself, but to any functional equivalent, such as the anhydride, acyl chloride, the acid salt, such as sodium hydrogen phthalate, amylamine hydrogen phthalate, ammonium hydrogen phthalate, benzylamine hydrogen phthalate, cyclohexylamine hydrogen "phthalate, ethanolamine-hydrogen phthalate,

diethanolamine hydrogen phthalate, triethanolamine hydrogen phthalate, or the acid esters such as ethyl hydrogen phthalate, propyl hydrogen phthalate, butyl hydrogen phthalate, ethylene glycol hydrogen phthalate, dihydroz-w propyl hydrogen phthalate, etc.

Attention is directed to the fact that the word amidification has been applied to the reaction involving the replacement of an amino hydrogen atom by an acyl radical without conventional limitation to a reaction involving ammonia. The replacement of the amino hydrogen atom of a primary amine or a secondary amine by an'acyl radical has been considered as being amidification, rather than the formation of a substituted amide, or the formation of an imide or substituted imide. Such obvious departure from conventional nomenclature has been for purposes of simplicity and to show the similarity between certain reactions.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, suchas water, petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract, obtained in the refining of petroleum, etc.', may be employed as diluents. Similarly, the material orv composition herein .described may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or composition may be used alone or in admixture with other suitable well known classes of demulsifying agents.

It is wellknown that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a-form' exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited water solubility and relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, lie-- cause said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or composition herein described.

We desire to point out that the superiority of the reagent or demulsifying agent herein described is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventionaimixtures thereof. It is believed that the particular demulsiiying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsiiying agents heretofore available.

In using our improved demulsiiying agent to resolve a petroleum emulsion, said demulsitying agent is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways or by any of the various apcombination with other demulsifying procedure,

'the molal ratio of 1:1 and 1:3, at a temperature above the boiling point of water and below the point of decomposition; said last mentioned reaction being conducted in a manner to yield a substantial quantity of basic material in which the blown oil fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain by replacement of the hydrogen of at least one hydroxyl of the hydroxy amineby the acyl radical of the blown oil fatty acid radical; said first mentioned esterification reaction involving a polybasic carboxy acid and being conducted in a manner so as to react with at least one hydroxyl radical of the blown oil fatty acid radical which is a part of the same molecule containing the basic nitrogen atom. V

2. A composition of matter, comprising the products derived by esterification reaction between "(a) a polybasic carboxy acid, and (b) the hydroxylated product derived by an alcoholysis reaction between a blown oil and diethanolamine within the molal ratio of 1:1 and 1:3; at a temperature above the boiling point of water and below the point of decomposition; said last mentioned reaction being conducted in a manner to yield a substantial quantity of basic material in which the blown oil fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain by replacement of the hydrogen of at least one hydroxyl of the hydroxy amine by the acyl radical of the blown oil fatty acid radical; said first mentioned esterification reaction involving a polybasic carboxy acid and being conducted in amanner so as to react with at least one hydroxyl radical of the blown oil fatty acid radical which is a part of the same molecule containing the basic nitrogen atom. v

' 3. A composition of matter, comprising the products derived by esterification reaction between (a) a polybasic carboxy acid, and (b) the hydroxylated product derived by alcoholysis reaction between a blown castor oil and diethanolamine within the molal ratio of 1:1 and 1:3, at a temperature above the boiling point of water and below the point of decomposition; said last mentioned reaction being conducted in a manner to yield a substantial quantity of basic material in which the blown oil fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain by replacement of the hydrogen of at least one hydroxyl of the hydroxy amine by the acyl radical of the blown oil i'atty acid radical; said first mentioned esterification reaction involving a polybasic carboxy acid and bein conducted in a manner so as to react with at least one hydroxyl radical of the blown oil fatty acid radical which is a part of the same molecule containing the basic nitrogen atom.

4. A composition of matter, comprising the products derived by esterification reaction be-- tween (0) a polybasic carboxy acid, and (b) a chemical compound of the type indicated by the in which m is 1 or 2, m is,0 or 1, and m" is 1 or 2, with the proviso that m+m'+m"=3; 'I is volves at least one hydroxyl radical of a blown oil v fatty acid radical indicated by the symbol R.

5. A composition of matter, comprising the products derived by esterification reaction between (a) a polybasic carboxy acid, and (b) a chemical compound of the type indicated by the formula:

(aoooaki 1 i t; NH

in which T is a hydroxy alkyl radical and 3.000 is a blown oil fatty acid radical; said product being further characterized by the fact that the esterification reaction'with the aforementioned polybasic' carboxy acid involves at least one hydroxyi radical of a blown oil fatty acid radical indicated by the symbol R.

6. A composition ,of matter, comprising the products derived by esteriflcatlon reaction between (a) a polybasic carboxy acid, and (b) a chemical compound of the type indicated by the formula:

in which T is a hydroxy ethyl radical and R.COO is a blown oil fatty acid'radical; said product being further characterized by the fact that the esteriiication reaction with the aforementioned polybasic carboxy acid involves at least one bydroxyl radical of a blown oil fatty acid radical indicated by the symbol R.

7. A composition of matter, comprising the products derived byesteriflcation reaction between (a) a polybasic carboxy acid,.and (b) a chemical compound of the type indicated by the. formula:

in which T is a hydroxy ethyl radical and RG is a blown oil fatty acid radical; said product being further characterized by the fact that the esteriflcation reaction with the aforementioned polybasic carboxy acid involves 'at least one hydroxyl radical of the blown castor oil fatty acid radical indicated by the symbol R.

MELVIN DE GROQTE.

' BERNHARD KEISER.

CHARLES M. BLAIR, JR. 

